678187-55-8Relevant articles and documents
Non-Metal-Catalyzed Heterodehydrocoupling of Phosphines and Hydrosilanes: Mechanistic Studies of B(C6F5)3-Mediated Formation of P-Si Bonds
Wu, Lipeng,Chitnis, Saurabh S.,Jiao, Haijun,Annibale, Vincent T.,Manners, Ian
supporting information, p. 16780 - 16790 (2017/11/28)
Non-metal-catalyzed heterodehydrocoupling of primary and secondary phosphines (R1R2PH, R2 = H or R1) with hydrosilanes (R3R4R5SiH, R4, R5 = H or R3) to produce synthetically useful silylphosphines (R1R2P-SiR3R4R5) has been achieved using B(C6F5)3 as the catalyst (10 mol %, 100 °C). Kinetic studies demonstrated that the reaction is first-order in hydrosilane and B(C6F5)3 but zero-order in phosphine. Control experiments, DFT calculations, and DOSY NMR studies suggest that a R1R2HP·B(C6F5)3 adduct is initially formed and undergoes partial dissociation to form an "encounter complex". The latter mediates frustrated Lewis pair type Si-H bond activation of the silane substrates. We also found that B(C6F5)3 catalyzes the homodehydrocoupling of primary phosphines to form cyclic phosphine rings and the first example of a non-metal-catalyzed hydrosilylation of P-P bonds to produce silylphosphines (R1R2P-SiR3R4R5). Moreover, the introduction of PhCN to the reactions involving secondary phosphines with hydrosilanes allowed the heterodehydrocoupling reaction to proceed efficiently under much milder conditions (1.0 mol % B(C6F5)3 at 25 °C). Mechanistic studies, as well as DFT calculations, revealed that PhCN plays a key mechanistic role in facilitating the dehydrocoupling reactions rather than simply functioning as H2-acceptor.
Activation of silylphosphines by diethyl azodicarboxylate: Novel silylation of alcohols
Hayashi, Minoru,Matsuura, Yutaka,Watanabe, Yutaka
, p. 1409 - 1411 (2007/10/03)
A novel activation mode of silylphosphines and an application of that to silylation of alcohols were described. Silylphosphines were found to be instantly activated by means of DEAD and PPTS to form reactive silyl cation equivalents. By using the activate